A mechanistic evaluation for total removal of toxic hexavalent and trivalent chromium from water by oxygen vacancy-engineered nanocomposite

Abstract

Oxygen vacancy-engineered nanocomposites are emerging materials in adsorption and photocatalysis research. This study evaluated total toxic Chromium removal by a nanocomposite of core-shell zeolite A@oxygen-vacant ZnO1−X (ZA@ZnO1−X) from water using its coexisting dual characteristics. ZA@ZnO1−X has removed 98.3% of total Cr, achieving a discharge limit of 0.05 ppm of Cr(VI) after the photoreduction and adsorption simultaneously. The detailed structural and physicochemical properties of synthesized ZA@ZnO1−X nanocomposite show higher BET surface area, oxygen-vacant percentage, and visible light photoactivity than the sole ZnO1−X nanosheet. The photocatalytic reduction efficiency (PRE) effect is systematically studied on varying operational variables like pH, citric acid (CA), Cr(VI) concentration, catalyst load, presence of anions, and radical scavengers. ZA@ZnO1−X removed Cr(VI) and Cr(III) simultaneously by 98.5% PRE with a catalyst load of 4 g/l, CA= 5 mM, pH= 5.06 under halogen light irradiation (300 W, 240 V) for 50 mins. This experimental study evaluates the prominent role of oxygen vacancy of ZA@ZnO1−X for photocatalytic reduction of Cr(VI) and enhanced adsorption of Cr(III). The kinetic study reveals adsorption of both Cr(VI) and Cr(III) follows pseudo-second-order kinetics, whereas photoreduction of Cr(VI) follows pseudo-first-order kinetics. A possible mechanism of total Cr removal is sketched, supporting enhanced adsorption due to unsaturated Zn atoms and unpaired e- at the oxygen defect site, followed by photoreduction by photogenerated e- and CO2-• radical. The ZA@ZnO1−X performance is reduced by only 2.5% after five consecutive runs without deformation. The easy regeneration process makes it suitable for toxic total Cr removal, avoiding any secondary pollution.